US3937680A - Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids - Google Patents

Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids Download PDF

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Publication number
US3937680A
US3937680A US05/364,532 US36453273A US3937680A US 3937680 A US3937680 A US 3937680A US 36453273 A US36453273 A US 36453273A US 3937680 A US3937680 A US 3937680A
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weight
hydrogel
terpolymer
hydrophilic
vinyl
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John Trevor de Carle
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Cooper Companies Inc
Global Vision Inc
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Global Vision Inc
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Priority to US05/364,532 priority Critical patent/US3937680A/en
Priority to CA201,017A priority patent/CA999399A/en
Priority to BE144885A priority patent/BE815694A/xx
Priority to FR7418693A priority patent/FR2231687B1/fr
Priority to NLAANVRAGE7407217,A priority patent/NL180320C/nl
Priority to GB2380974A priority patent/GB1475605A/en
Priority to DE2426147A priority patent/DE2426147C2/de
Priority to JP5982174A priority patent/JPS5533048B2/ja
Priority to ES426728A priority patent/ES426728A1/es
Priority to IT23679/74A priority patent/IT1019641B/it
Publication of US3937680A publication Critical patent/US3937680A/en
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Assigned to DAIWA BANK, LIMITED, LOS ANGELES AGENCY, THE, A BANK OF JAPAN reassignment DAIWA BANK, LIMITED, LOS ANGELES AGENCY, THE, A BANK OF JAPAN SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COOPER COMPANIES, INC., THE
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/916—Hydrogel compositions

Definitions

  • This invention is directed to hydrophilic terpolymers and to shaped hydrogel articles, especially contact lenses, produced therefrom.
  • the amount of water which such hydrophilic polymers are capable of retaining is, as stated by Wichterle, inversely proportional to the degree of crosslinking so that the hydrogels having a high water content can only be obtained when the extent of crosslinking is very small.
  • Other compositions including polyvinylpyrrolidone (PVP) graft copolymers have been developed for contact lenses but the significant solubility of the PVP structure in water over a relatively short period of time has created undesirable characteristics in such lenses.
  • PVP polyvinylpyrrolidone
  • 3,532,679 to Steckler discloses a crosslinked copolymer comprising a vinyl lactam and an acrylic ester monomer, but the amount of lactam required in the composition is so high as to affect the mechanical properties of the resulting lens product, which is described as containing up to 95% water.
  • High water content contact lenses such as proposed by Wichterle and Steckler are characterized by relatively high rates of transmission of gaseous metabolites to and from the cornea but this positive feature is countered by their poor mechanical properties.
  • Hydrophilic contact lenses having less than 50% water content have good mechanical properties but do not exhibit sufficiently high oxygen transmission characteristics to facilitate permanent wear. Thus, in order to prevent anoxic edema such lenses must be removed during non-waking hours.
  • polymeric hydrogels having high water contents in the range of about 55% to about 85% which are particularly suitable for contact lenses can be produced from crosslinked terpolymers which in their broadest aspect comprise the reaction product of a hydroxyalkyl acrylate or methacrylate, a heterocyclic N-vinyl monomer, a polymerizable unsaturated carboxylic acid and a crosslinking monomer such as a glycol dimethacrylate or diacrylate.
  • the terpolymer of this invention is formed by polymerizing about 30-50% by weight of heterocyclic N-vinyl monomer, up to about 3% of a glycol dimethacrylate or diacrylate crosslinking agent, between about 0.25-5.6% by weight unsaturated carboxylic acid, and hydroxyalkyl acrylate or methacrylate which constitutes the balance of the mixture.
  • Hydrogels formed by contacting such a terpolymer with an aqueous alkaline solution have a water content between about 55-85% by weight.
  • N-vinyl lactams such as N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone and N-vinyl-e-caprolactam.
  • suitable compounds include N-vinylimidazolidone, N-vinyl succinimide and the like.
  • N-vinyl monomers are commercially available and produced by well known methods.
  • the higher water capacity of the hydrogels is due to the presence of the carboxylic groups which are attached to or incorporated in the polymer chain.
  • Contact lenses made from the terpolymers of the present invention have been shown to possess high oxygen and metabolite transmission characteristics which leads to a high degree of toleration by lens wearers who have stressed their comfort and ease of adaptation to the lenses. It is believed that this compatibility of the lenses with the human eye may be at least partially due to the close similarity in the water content of the lenses and cornea of the human eye since the eye contains a very high percentage of water, variously estimated at between about 72% and 81% by weight.
  • the lenses of the present invention have a percentage water content approximating this range, although lenses having a water content between about 60% and 80% have been found to be very satisfactory.
  • a degree of crosslinking of the terpolymer is necessary to form a three-dimensional polymer skeleton in which water can be accommodated.
  • increasing the degree of crosslinking tends to reduce the water holding capacity while at the same time increasing the rigidity and strength of the hydrogel.
  • Reduction in water holding capacity arising from a higher degree of crosslinking can be offset to some extent by increasing the proportion of the vinyl pyrrolidone component or other vinyl comonomer, but this is accompanied by undesirable changes in mechanical properties.
  • crosslinking material such as glycol diacrylates, glycol dimethacrylates (including ethylene and propylene glycol diacrylates and methacrylates), polyethylene glycol diacrylates and dimethacrylates and allyl methacrylate.
  • Tri- or polyfunctional monomers such as triallyl cyanurates may also be utilized as crosslinking agents with considerable effectiveness.
  • an additional effect of increasing the proportion of vinyl pyrrolidone is to reduce the mechanical strength of the polymer.
  • the proportion of vinyl pyrrolidone and the degree of crosslinking have to be balanced to obtain the desired product.
  • the amount of vinyl pyrrolidone will not exceed 60% and will preferably constitute between about 30-50% by weight of the total.
  • VP vinyl pyrrolidone
  • the terpolymer will contain at least about 10% VP based on the total weight thereof.
  • hydroxyalkyl acrylate or methacrylate is not critical and satisfactory results may be achieved using acrylates and methacrylates in which the alkyl groups contain from 1 to 4 carbon atoms, although the hydroxyethyl and hydroxypropyl compounds are preferred.
  • the third principal monomeric component of the terpolymers of the invention is a polymerizable, unsaturated carboxylic acid. While present in a comparatively minor proportion, this constituent is important in increasing the water holding capacity of the terpolymer when exposed to alkaline solutions.
  • the preferred compounds in this category are methacrylic acid and acrylic acid which are incorporated in amounts ranging from 0.25-5.6% by weight of the total.
  • the carboxylic acid moieties in the terpolymer impart a substantial effect on equilibrium water content of the hydrogel.
  • a terpolymer specimen as previously described, made with 3.5% methacrylic acid (MA) by weight of the total in the monomer mixture equilibrated to a water content of about 80% by weight in alkaline solution; whereas a comparable specimen formed without MA equilibrated to about 60% by weight in the same alkaline solution.
  • the higher water content capability of the carboxylic acid moiety containing terpolymer is achieved only by conversion of the free carboxylic acid groups in the hydrogel to ionized carboxylate groups, such as the Na, K, Ca, NH 3 and Mg forms.
  • conversion is effected through treatment of the terpolymer by an aqueous solution reactive with the free carboxylic acid groups, notably treatment with an alkaline aqueous solution.
  • the conversion may be effected by equilibrating the terpolymer with a buffered aqueous solution of pH 6 or higher. Comparable treatment with de-ionized water or isotonic saline will not hydrate the terpolymer beyond the levels obtained without any MA content. Indeed, absent an alkaline conversion treatment, the presence of a carboxylic acid moiety seems to nominally decrease the water retention capability of the terpolymer hydrogel.
  • treatment is with buffered aqueous sodium bicarbonate, carbonate or hydroxide.
  • Treatment may also be with a conventional alkaline biocide solution.
  • test specimens exhibited far greater water retention levels than like specimens equilibrated in 0.9% saline (76 wt % as compared to 57 wt %).
  • Treatment of the test specimens with 5% HCl reduced their water retention capability to about the level of the 0.9% saline equilibrated specimens (to 60 wt %).
  • the highly ionized hydrogen ions of HCl readily displaced the metallic ions because of the favorable equilibrium to the virtually unionized free carboxylic form. Conversion of strongly ionic groups to weakly ionic groups causes desorption of significant amounts of H 2 O. Subsequently, equilibrating in the buffered alkaline aqueous solution increased the water retention capability to the previous level.
  • the N-vinyl monomer e.g. vinyl pyrrolidone
  • the N-vinyl monomer may be present in the polymerization mixture in a proportion of from 10-60% by weight of the total.
  • the polymerization mixture contains acrylic acid or methacrylic acid in amounts between 0.25-5.6%, preferably 1.25-2.8% by weight, based on the total, the amount of vinyl pyrrolidone utilized in the mixture will be between about 30-50% by weight, preferably 35-45% by weight.
  • the preferred hydrogel terpolymer compositions will be formed from a polymerization reaction mixture containing hydroxyethyl methacrylate (HEMA), vinyl pyrrolidone (VP), methacrylic acid (MA), and ethylene glycol dimethacrylate (Di-Ester).
  • HEMA hydroxyethyl methacrylate
  • VP vinyl pyrrolidone
  • MA methacrylic acid
  • DI-Ester ethylene glycol dimethacrylate
  • the hydrophilic polymer In the manufacture of the hydrophilic polymer, it is preferred to use mild conditions and carry out polymerization at a relatively low temperature and over an extended period. It is believed that this results in a product having better properties.
  • the monomers are mixed together without a solvent or dispersant, but with no more than 1% of total weight of a conventional addition polymerization catalyst, e.g. a peroxy free-radical catalyst, and filled into a polyethylene container and held at a temperature of about 50° to 75°C. for several hours.
  • a conventional addition polymerization catalyst e.g. a peroxy free-radical catalyst
  • a rod of solid polymer can be removed from the tube and sliced into discs of the desired size for use as contact lens blanks in the manufacture of the contact lenses.
  • the polymerization may be carried out in polyethylene molds of desired shape, thus producing preformed blanks for subsequent lens manufacture.
  • the blanks so obtained are slightly soft and are heated for about a day at about 75°C to 100°C. in order to complete the polymerization or crosslinking reactions and to produce contact lens blanks which are hard enough to be cut and polished using conventional contact lens cutting and polishing techniques.
  • the two-stage polymerization process is desirable because if one attempts to heat the polymerization reaction mixture initially to a temperature above about 75°C., bubbles may tend to form and are retained in the resultant polymer.
  • the lenses are water extracted in a Soxhlet apparatus for an extended period of time, e.g. 24 hours.
  • the preferred lenses, prepared according to the examples set forth hereafter, will have a water content, after equilibrium in an isotonic saline solution of 0.9% concentration by weight, of about 54% and when similarly equilibrated following extraction in a Soxhlet apparatus for 24 hours, a water content of about 57% by weight. However, subsequent to equilibration with an alkaline aqueous solution, the water content will be about 75% by weight.
  • Treatment of the lenses to form alkali carboxylate salt moieties thereon need not be deferred until after the extraction treatment. It may be effected at any time subsequent to the initial hydration, as for example, before, or even during, the course of extraction treatment. If the extracted lenses are also treated with a biocidal solution, such treatment may be combined with the alkaline treatment. Indeed, some proprietary biocidal compositions are themselves buffered, mildly alkaline solutions. Thereafter, the lenses may be washed and stored in a mildly alkaline isotonic saline or in a biocidal solution. The lenses should be so kept, because they dry out relatively quickly when not in contact with an aqueous fluid, as do conventional lenses.
  • the lenses of the present invention may be sterilized by boiling in water without deterioration of the terpolymer. However, it has been found in practice that the lenses of the invention do not require routine sterilization in normal use.
  • a polymerization mixture was prepared by mixing 57.8% by weight of 2-hydroxyethyl methacrylate (HEMA) with 40% by weight of N-vinyl pyrrolidone, 1.7% by weight of ethylene glycol dimethacrylate, 0.5% by weight methacrylic acid and 1% by weight of benzoyl peroxide was subsequently added to the mixture.
  • the polymerization mixture was poured into small shaped molds. By inserting the molds in a thermostatically controlled oven, the reaction temperature was maintained at about 75°C. and the reaction was allowed to proceed for 5 hours. After this time, the oven temperature was raised 100°C. for a further period of 24 hours.
  • the blanks were, after cooling, removed from the molds and cut and polished in the normal way. Thereafter, the lenses were extracted (24 hours in a Soxhlet).
  • the soft lenses When treated with an alkaline pH 9 biocidal preparation applicable to contact lenses by immersion to equilibrium water intake, the soft lenses were found to have water contents of about 70-75% by weight.
  • a series of lens sized test specimens were made according to the above described procedure (including 24 hours Soxhlet extraction) with the same monomer proportions, varying only the methacrylic acid from 0-7% and a proportionate amount of HEMA.
  • the extracted specimens were then treated in two ways; one set was equilibrated in a buffered alkaline saline solution and the other in isotonic saline, then washed with water.
  • a series of crosslinked terpolymer specimens were prepared with varying percentages of vinyl pyrrolidone in the monomer mixture.
  • methacrylic acid was 2% by weight of the total monomer
  • ethylene glycol dimethacrylate was 0.8% by weight of the total monomer
  • the catalyst CYCLONOX LE-50 cyclohexanone peroxide sold by Novadel, Ltd., Peroxide Division
  • HEMA was the balance.
  • the polymerization was effected by heating 48 hours at 80°C. in a nitrogen atmosphere.
  • a series of terpolymer test specimens were prepared from a monomer mixture of 3:2 volume ratio HEMA/VP.
  • the HEMA contained methacrylic acid and 0.8% ethylene glycol dimethacrylate.
  • the polymerization catalyst and conditions of Example 1 were employed.
  • test specimens were equilibrated in buffered aqueous solutions at various pHs, then the water content measured. The results are tabulated below.
  • Specimens prepared as described in Example IV were treated as follows after water extraction.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US05/364,532 1973-05-29 1973-05-29 Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids Expired - Lifetime US3937680A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US05/364,532 US3937680A (en) 1973-05-29 1973-05-29 Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids
CA201,017A CA999399A (en) 1973-05-29 1974-05-28 Contact lenses
ES426728A ES426728A1 (es) 1973-05-29 1974-05-29 Procedimiento para la fabricacion de lentillas de contacto de hidrogel.
FR7418693A FR2231687B1 (nl) 1973-05-29 1974-05-29
NLAANVRAGE7407217,A NL180320C (nl) 1973-05-29 1974-05-29 Werkwijze voor de bereiding van een polymeer hydrogel, werkwijze voor het vervaardigen van een hydrogel contactlens, alsmede aldus verkregen contactlens.
GB2380974A GB1475605A (en) 1973-05-29 1974-05-29 Hydrogels and contact lenses formed therefrom
DE2426147A DE2426147C2 (de) 1973-05-29 1974-05-29 Polymeres Hydrogel und dessen Verwendung zur Herstellung von Kontaktlinsen
JP5982174A JPS5533048B2 (nl) 1973-05-29 1974-05-29
BE144885A BE815694A (fr) 1973-05-29 1974-05-29 Prothese oculaires de contact
IT23679/74A IT1019641B (it) 1973-05-29 1974-06-06 Perfezionamenti nelle e relativi alle lenti a contatto

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US05/364,532 US3937680A (en) 1973-05-29 1973-05-29 Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids

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US05223122 Continuation-In-Part 1972-02-03

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US (1) US3937680A (nl)
JP (1) JPS5533048B2 (nl)
BE (1) BE815694A (nl)
CA (1) CA999399A (nl)
DE (1) DE2426147C2 (nl)
ES (1) ES426728A1 (nl)
FR (1) FR2231687B1 (nl)
GB (1) GB1475605A (nl)
IT (1) IT1019641B (nl)
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US4123407A (en) * 1976-11-26 1978-10-31 American Optical Corporation Hydrophilic contact lens
US4124555A (en) * 1978-01-10 1978-11-07 The Goodyear Tire & Rubber Company Water reducible coating compositions containing copolymers of vinyl pyrrolidone and unsaturated carboxylic acid and containing a solvent and a volatile amine
US4139692A (en) * 1977-10-12 1979-02-13 Toyo Contact Lens Co., Ltd. Copolymer for contact lens, its preparation and contact lens made thereof
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US4158089A (en) * 1977-12-27 1979-06-12 Wesley-Jessen Inc. Contact lenses of high water content
US4182802A (en) * 1977-12-27 1980-01-08 Samuel Loshaek Hydrophilic polymers and contact lenses of high water content
DE3023096A1 (de) * 1979-06-25 1981-01-08 American Optical Corp Kontaktlinsenmaterial und verfahren zu dessen herstellung
US4272422A (en) * 1978-08-16 1981-06-09 Japan Exlan Company Limited Aqueous microhydrogel dispersions, processes for producing the same, and processes for producing microhydrogels
FR2470638A1 (fr) * 1979-12-05 1981-06-12 Kendall & Co Composition absorbant l'eau, catheter, suture ou plaque de verre enduits de cette composition
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US12257184B2 (en) 2019-10-24 2025-03-25 Denis LaBombard Ocular device and drug delivery system, with case

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JP2543334B2 (ja) * 1985-03-11 1996-10-16 ホ−ヤ株式会社 高含水コンタクトレンズ
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BE815694A (fr) 1974-09-16
GB1475605A (en) 1977-06-01
ES426728A1 (es) 1977-01-01
FR2231687B1 (nl) 1979-08-03
NL7407217A (nl) 1974-12-03
FR2231687A1 (nl) 1974-12-27
IT1019641B (it) 1977-11-30
JPS5042861A (nl) 1975-04-18
DE2426147C2 (de) 1983-04-28
NL180320B (nl) 1986-09-01
JPS5533048B2 (nl) 1980-08-28
DE2426147A1 (de) 1974-12-19
NL180320C (nl) 1987-02-02
CA999399A (en) 1976-11-02

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